Contacting solid particles with gaseous fluids



June 15, 1948. R. w. KREBs CONTACTING SOLID PARTICLES WITH GASEOIVJS FLUIDS lFiled laren 21, 1944 FIG. 2

STANDPIPE FIG. .3

FIG. I

Magi/m INVENToR ATTORNEY Patented 1MB i CONTACTING SOLID PARTICLES WITH vG'ASEOUS FLUIDS Robert W. Krebs, Baton Rouge,l La.,'asslgnor to Standard Oil Development Company, a corporation of Delaware Application Maren 21, 1944, serial No. 521,404

This invention relates to contacting gaseous fluids with divided solids. E

In certain catalytic reactions with organic compounds, combustible material is deposited on the catalyst or contact particles and the particles 5 Claims. '.Cl. 19.6-52) must be regenerated before being used overagain as a catalyst or contacting agent. In the catalytic cracking of hydrocarbons, coke or carbonaceous material is deposited on the catalyst parv of adsorbed hydrocarbons. 'Thine-hydrocarbonsA mayjfthen be separately condensed' and used as partj 'of'v the feed stock or they may be returned -jjin vaporform to the cracking zone or combined with the cracked products.

vccording to this invention;

"Y constricted, partially. obstructed, or provided with baiiles to vincrease the catalyst dispersion and decrease oilentrainment before the catalyst goes to one form vof vreactionvessel provided with my '5 thespent-catalys't particlesgare withdrawn from a cracking zone orcontacting zone and passed to a stripping zone before they are introduced. into a regeneration "zone: The entrancev to the strippingizone comprises-a relatively narrow passagewaywh'ichis 2 the stripping zone or main portion ping zone.

In the preferred form of the invention, the fouled or. spent catalyst leaves the .bottom of the of the stripreactor in a relatively dense iluidlzed or dry.

liquid-like'- condition, vand in order to prevent the entrainment of hydrocarbons in large masses of agglomerated catalystparticles'a stripping gas is passed through the fouled orspent cataticles and the fouled or spent catalyst particles 1i lyst as it is passed through the passageway and are-regenerated by burning with air or oxygenbefore it enters the stripping zone. containing gas, 'Ihe stripping gasis introduced yat one end of v v As the catalyst or contact particles are adsorb- -the passageway at a relatively high velocity to ent, they contain adsorbed hydrocarbons, and i form a lighter or less dense fluidized mixture of when the catalyst or contact particles are passed if) catalyst but, the velocity 0f the Bes iS insulclent to the'regeneration zone, the adsorbed hydrocarto force the catalyst particles upwardly into the boris are burned along with' the coke or carboreactionzone.l The catalyst particles flow down naceous material. As the burning gives off heat, through the passageway and into the stripping. the temperature during regeneration I nust be 2011. AdditiOnel Stripping gas is introduced into carefully controlled to prevent overheating of the the bottom portion 0f thestl'ipping Zeile Where catalyst particles; When the hydrocarbon feedmOSt'of the strlppingtakes place. "lhe velocity being cracked is a high coke-forming stock and 0f the additinaistl'ipping gas islow and th'e the fouled or spent catalyst particles contain adstripping time isrelatively 10118., Because of the `sorbed hydrocarbons inaddition to a large 10W velocity of the stripping 88S. the density 0f amount of coke or carbonaceous material, there the fluidized catalyst-undergoing Stripping in the is danger of overheating the contact or catalyst Stripping Zone i5' high and improvedstripping reparticles, Y suits from the long residence time in the stripper,

-Especially is this true Awhen the hot regener- Inthe above form ofthe invention, th'e stripated catalyst particles are,used in a sulcient ping gBSiS introduced into the Stripping zene amount to vaporize liquid oil orv partly liquid and through a pluralityof ports or holes in a perpartly vaporized oil-and to supply the heat of' forated false bottom.l The ports or holes are relcracking, as the cracking and regeneration zones atively Small' and at least 011e pert per square must 'be kept in heat balance where h'eat is not foot of cross sectional stripping area, is provided removed from the regeneration zone during the in the false bottom.

regeneration operation. Also, by having more 35 In another form of the invention, the narrow combustible material present on the catalyst or passageway, together with the constriction, ob-

' contactparticles, the time of regeneration is in- Struetiorl, 0r bellies, iS eliminated and only the creased... perforated falsefbottom is used for introducing Preferably, the fouled or spent catalyst is Stripping gas into the bottom of the stripping 'stripped with a stripping gas i-,opurge the cata- 40 Z0r1e` Aly'st or contact particles or strip these particles inthe dr8WiI l8.

Fig. 1 represents a vertical cross-'section of stripping zone;

. Fig. v2 represents 'a horizontal cross-section taken substantially on line 2-2 of Fig. 1-; vand I` Fig.- 3 represents another form of my invention including a vessel provided with a stripping zone- Referring now to Fig. 1 of the drawing, the reference character i0 designates a. reaction vessel having a top' outlet I2 for vaporous products or reaction products anda bottom outlet Il for stripped catalyst. 'I'he outlet i4 forms a part lregeneration zone (not shown).

a Y of a standpipe for building up .hydrostatic pressurewith the fluidized stripped catalyst particles for forcing the catalyst particles into a The reaction vessel I6 is provided with an inlet pipe I6 into which hot regenerated catalyst or contact particles are introduced from line. I8 below valve 22. Standpipe 24 is provided with the valve 22 for controlling the amountof catalyst being discharged into the line I8. Only a portion of the standpipe' 24 is shown but it will be understood that the standpipe is full of iiuidized regenerated hot catalyst particles which produce a. hydrostatic pressureat the base of the standpipe 24 sufcient to force a less densey catalyst-gaseous mixture through line I6 and through the reaction vessel I0.

Liquid or vaporous reactants are introduced into line I6 through line 26. Wherethe reactants are liquid, a suilicient amount of hot regenerated catalyst or contact particles is used to vaporize the liquid reactants and supply the heat of reaction where the reaction is endothermic. Where the reactants are in vapor form and at reaction temperature, a small amount of catalyst or contact particles may be used.

The invention is especially adapted for useV in 4the catalytic cracking of hydrocarbons in which the hydrocarbon oil in liquid or vaporized form is introduced through line 264 and mixed with hot regenerated catalyst from the standpipe 24. Any suitable cracking catalyst may be used, such as acid-treated bentonite clays, syn'thetic silica alumina, gels, synthetic silica magnesia gels, etc. The catalyst is preferably in powdered form having a size of about 200 to 400 mesh or ilner. `Sufficient hydrocarbon oil is introduced through line 26 to produce a less dense catalyst-gaseous iluid mixture in line I6 so that the hydrostatic pressure developed by standpipe 24 moves the catalyst and hydrocarbon vapors upwardly through line I6. I

-The inner end ofpipe or line I6 is enlarged as shown at .28 and is provided with agrid or dis. tributionmember 32. rlfhe venlarged end 28 is arranged in the lower portion of the reaction vessel |0. The grid member 32 is preferably circular and has a smaller diameter than .the internal diameter of the reaction vessel I0. The grid member 32 functions to distribute the catalyst particlesand vapors evenly across the crosssectional area of the reaction vessel III.

The velocity of the hydrocarbon Avapors or gases is so selected that the catalyst or contact particles are maintained in a dry iluidized condition in 'the reaction vessel. I0. and a bed of iiuidized mixture is formed as shown at 34 with a level 36. In .this condition the dry fluidized mixture assumes many of the characteristics of a liquid, and in addition, the catalyst particlesvare maintained in a turbulent condition so that extremely good mixing and contacting between the gases and vapors and catalyst or contact particles is eiected.

The gases o'r vapors lpassing upwardly through the bed 34 of iluidiz'ed catalyst are converted to desired products and the vaporous reaction products pass upwardly into the space 38 above the dense bed of catalyst. In the space 38 the reaction products in vapor form contain entrained catalyst particles but the mixture is much less dense and is referred to as the dilute phase.

When using 200 to 400 mesh acid-treated bentonite clay .and with a velocity of the vapors or gases in the space 38 of about 0.5 ft./Se0nd 4 to 1.5 ftJsecond, the density of the iiuidized mixture shown at 34 is about `15 iba/cu. It.' to 30 iba/cu. ft.

The vaporous reaction products from the space 32 in the reaction vessel I6 pass through sepa.

rating means 42 which is arranged in the upper portion of the reaction vessel I8. The separatingmeans 42 is shown as a cyclone separator but other forms of separating means may be used.

The separated catalyst particles are collected in the bottom of the separating means 42 and are returned to the bed of iluidized catalyst particles 34' through line 44 which extends below the level -isired fractions or products. These vaporous reaction products contain a small amount of entrained catalyst or vcontact particles and may be passed through additional separating means if desired. When cracking hydrocarbon oils, the

vaporous reaction products passing through line I2 are passed to a fractionating towerwherein heavy ends of the cracked products arejcondensed and all of the entrained catalyst particles are washed out of the reaction vapors and recovered in a. slurry in the bottom of the lfractionating tower..

In the catalytic conversion of coke or carbonaceous material is deposited on the catalyst particles and it is necessary to regenerate the catalyst particles .before using them Ain another conversion operation. Also the catalyst particles areadsorbe'nt and adsorb hydrocarbon vapors or liquids. particles are usually regenerated by burning the coke or carbonaceous material with air in a regeneration zone. When the coke or carbonaceous. material is burned, any adsorbed hydrocarbons are also burned and lost. In some cases too much heat is produced in the regeneration zone by large deposits of coke or carbonaceous material on the catalyst particles, and where these catalyst particles also containvadsorbed oil, it is Anecessary to control the temperature` during reway 48 leading from the bottom of the reactionv vessel I0 to the stripping zone 46. The relatively -narrow passageway. is bounded on one side by collar or annular ange 52 which is attached to the lower part of thegrid member 32 and which has a smaller diameter than the inner wall of the vessel I0. The relatively narrow passageway 48 is formed between the collar or flange 52 and the wall 54 of the reactionvesslei I0.

In order to. prevent the entrainment. of oil vapors in large masses of agglomeratedcatalyst hydrocarbons,

The spent or fouled catalyst g viding the annular bellies I6 in the passageway 4l, additional mixing between'the stripping gas and the fouled or spent catalyst is obtained. Stripping gas may be introduced into the bottom portion of the passageway 4l through inlet lines 62 which are shown at opposite sides of the reaction vessel I0. Preferably` at least four of these inlet lines are used but more or less of them may be used as desired. l

The strippinggas introduced through lines I2 passes upwardly through the narrow passageway 46 at a much higher velocity than the vapors and gases pass through the dense iluidized bed 34 of catalyst in the reaction` vessell Il. However, the velocity of the stripping gas is so selected that downward flow ofthe spent catalyst from the mass 34 is not prevented-, For example,

when using steam as a stripping gas, the velocity may be as high as 3 ft./second at 150 lbs. per minute per square foot of downward catalyst ilow when using synthetic silica alumina catalyst of 200 to 400 standard mesh and 14% 0 to 20 micron particles. Under these conditions, the spent or fouled catalyst will ilow downwardly through the passageway 46 to vmain stripping zone 46. Instead of using bailles 56, the passageway may be provided with other constrictions such as spaced perforated plates. Y y

The narrow passageway 46 conducts the spent or fouled catalyst particles to the stripping zone.

46. The stripping zone 46 is formed by a conical false bottom 64 provided with openings 65. The false bottom 64 is spaced as at 65' from the conical bottom 66 of the reaction vessel I6. One or more inlet lines 68 are provided for the introduction of stripping gas, such as steam, light hydrocarbon gas or inert gas, into the space 65' beneath the false bottom 64. The introduced stripping gas has a lower velocity in the stripping zone 46 than in the narrow passageway 46. Because of the lower velocity, the density of the fluidized catalyst particles being stripped in the stripping zone 46 .is relatively high. The density of the iluidized mixture undergoing stripping when using silica alumina synthetic gel in powdered form is about lbs/cu. ft. to 40 lbs/cu. ft. Also, because the velocity in the stripping zone 46 is low, the steam or stripping gas consumption will be low, thus effecting considerable economy.

I have found that improved results are obtained in the stripping zone when there is a certain relationship between the size and numbervof the holes and the cross-sectional strippingv area. With the holes of about 0.007 sq. ft. in crosssectional area, atleast one hole per square foot of cross-sectional stripping area is preferred. The area of the lholes may vary from about 0.005 lto 0.02 sq. ft. The velocity of they stripping gas passing through the stripping zone 461s about 0.5 ft./second to 1.5 ft./second. The holes 65 ensure uniform distribution of the stripping gas.

soA

In the form of the invention shown in Fig. 1

Y, rately introduced into the reactionvessel Il.

Referring now to Fig. 3. the referencel character l2 designates a vessel provided with a. perforated false bottom I4 similar to the false bottom 44 described in connection with Fig. 1. The false bottom is arranged at a distance from the conical bottom Il of the vessel 82 and forms espace i4 into which stripping gas is introduced through line or lines I2. The conical false bottom I4 is provided with openings or` holes Il. The conical bottom and conical false bottom shown in Fig. 3 functions in substantiallythe same way as the same construction does in Fig. 1 and vfurther description oi' this construction is not necessary.

In Fig. 3 the narrow passageway shown at 48 in Fig. 1 has been' omitted. The vessel 62 may be a reaction vessel similar to that shown in Fig. 1 wherein catalyst or contact particles and reactants are introduced intothe vessel and maintained as a relatively dense dry fluidized mixture in which vaporous reaction products pass overhead and fouled or spent catalyst is with-v drawn in a relatively dense condition from the bottom of the vessel.

As shown in Fig. 3, the vessel 62 is a stripping vessel or hopper provided with a bottom stripping zone comprising the false bottom I4. 'I'he reaction products in vapor form containing entrained catalyst particles are passed through line 94 to separating means 96 in which the catalyst particles are separated from vaporous reaction products. The vaporous reaction products pass overhead through line 96 from the separating means and to any desired separating equipment such as a fractionating equipment.

The separated catalyst particles are collected in the separating means 96 and are passed through line |02 to vessel 82 below the level |04 of iluidized powdered solids |06. In this lform of the invention the stripping gas introduced through line or lines 92 is selected to maintain the catalyst particles in a relatively dense condition having many of the properties of a liquid Instead of passing the reaction products andv spent catalyst to separator 96, the hopper or vessel 22 may be arranged below a reaction vessel (not shown) so that spent catalyst in a more or less dense phase is passed directly from the reaction zone into hopper or vessel ,62.

In the form of the invention shown in Fig. 3, .the holes or'perforations 9.3 in the false bottom 64 have an area of about 0.007 square foot andy the velocity of. thestripping gas passing upwardly through the nuidized bed |66 is about 0.5 foot per second to 1.5 feet per second. For best stripping results, at least one hole or ropening per square vfoot of cross-sectional stripping area is required.

lThe following data show the improvement-rei sulting from increasing the stripping gas velocity at the entrance to the stripping zone. Both sets of am. were obtained at 0.6 ft./sec.ve1ocity and 0.5 minute in the main portion of the stripping reaction.

zone, but in 'the latter case the velocity was v2.1 ft'./sec. in thel entrance to the stripping zo'ne. i

Velocity at Entrance 0.6 ftJsec. 2.1"ft'/scc. I

Per cent Strip able Hydrocarbon'rc- A l l'niainintz on Jataiyst 0.12" 0.04

l A j My invention is especially adapted for remov-A 1'. "A method of converting hydrocarbons which comprises introducing divided catalyst particles andl hydrocarbons into a 'reaction zone, contactving the catalyst particles l' with hydrocarbon vapors in said reaction zone and forminga rela; tively dense dry iiuidized mixture having a level in said reaction zone., flowing fouled catalyst particles in a dry tlu'idize'd condition' from the bottom "of said'reaction zoneinto a restricted passageway, continuously introducing a gas into the bottom portion of 'saidpassagewayvso that the gas ows upwardly countercurrent ata re'la.-

tively high velocity to the downflowing catalyst particles, then passing the catalyst 4particles into" an enlarged stripping zone, introducing strip; ping gas into the bottom portion'jof said enlarged zone at a plurality o'f 'points and at a lower velocity than in said passageway to remove hy,-y drocarbon vapors from the fouled catalyst p ar'- ticles, passing the last mentioned removed hy-ll drocarbons from said stripping zone and withdrawing stripped catalyst from the bottom portion 'of said enlarged zone.

2. A method according to claim 1 wherein the stripping gas is introduced into said enlarged zone through a plurality of'ports which are arranged so that there is atleast one port per s'quare foot of cross-sectional stripping area.

3. A method according to claim 1 wherein the stripping gas is introduced into said enlarged zone through a plurality of ports whichv are arranged so that there is about one vport per square i 5f' foot of cross-sectional stripping area and theV port has an area oi.' about 0.007 square foot'.

4. An apparatus of the character described in' cluding a vessel provided with a top outlet and a bottom outlet, means forintroducing ailuid and divided contact particles into said' vessel, said means including a grid member spaced fromthe inner wall of said vessel to provide a. passageway, a stripping section in saldi-vessel and below said grid member, bailles in sai'd pasf' sageway, said passageway forming part of the ROBERT W. KREBS.

' REFERENCES CITED,

. rllher'following references are of record in the, file of. this patent:

t UNiT'ED STATES PATENTS Number Name v Date 1,334,2354 Eckhardt Mar. 16, 1920, '2,079,158 DeRachat May 4, 1937 '2,239,801' Voorhees Apr. 29, 1941 2,310,377 Voorhees Feb. 9, 1943 2,316,195 Troxler Apr. 13, 1943`4 2,320,318 Simpson et al. May 25, 1943' 2,336,017 Jewell et al Dec. 7, 1943, 2,337,684 Scheineman Dec. 28, 1943 2,340,878 Holt et al. Feb. 8,1944 '2,367,281 Johnson' Sept. 30. 1941 2,367,694 Snuggs Jan. 23', 1945 2,391,944 Carlsmith Jani, 1946' 2,394,814 Snuggs 1I Feb. 12, 1946 

